|Publication number||US5480572 A|
|Application number||US 08/242,749|
|Publication date||Jan 2, 1996|
|Filing date||May 13, 1994|
|Priority date||Jun 16, 1993|
|Also published as||EP0703953A1, WO1994029402A1|
|Publication number||08242749, 242749, US 5480572 A, US 5480572A, US-A-5480572, US5480572 A, US5480572A|
|Inventors||Barbara H. Minor|
|Original Assignee||E. I. Du Pont De Nemours And Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (16), Non-Patent Citations (6), Referenced by (27), Classifications (37), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part of U.S. patent application Ser. No. 08/077,353, filed Jun. 16, 1993, now abandoned.
This invention relates to refrigerant compositions that include at least one three carbon cyclic fluoroether. These compositions are useful as cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
Fluorinated hydrocarbons have many uses, one of which is as a refrigerant. Such refrigerants include trichlorofluoromethane (CFC-11) dichlorodifluoromethane (CFC-12) and chlorodifluoromethane (HCFC-22).
In recent years it has been pointed out that certain kinds of fluorinated hydrocarbon refrigerants released into the atmosphere may adversely affect the stratospheric ozone layer. Although this proposition has not yet been completely established, there is a movement toward the control of the use and the production of certain chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) under an international agreement.
Accordingly, there is a demand for the development of refrigerants that have a lower ozone depletion potential than existing refrigerants while still achieving an acceptable performance in refrigeration applications.
In refrigeration applications, a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere during maintenance procedures on refrigeration equipment. If the refrigerant is not a pure component or an azeotropic or azeotrope-like composition, the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment, which may cause the refrigerant to become flammable or to have poor refrigeration performance.
Accordingly, it is desirable, if possible, to use as a refrigerant a single compound or an azeotropic or azeotrope-like composition of more than one compound.
It is also desirable to find replacements for CFCs and HCFCs for use as a cleaning agent or solvent to clean, for example, electronic circuit boards. It is preferred that the cleaning agents be azeotropic or azeotrope-like because in vapor degreasing operations the cleaning agent is generally redistilled and reused for final rinse cleaning.
Replacements for CFCs and HCFCs may also useful as blowing agents in the manufacture of closed-cell polyurethane, phenolic and thermoplastic foams, as propellants in aerosols, as heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids such as for heat pumps, inert media for polymerization reactions, fluids for removing particulates from metal surfaces, as carrier fluids that may be used, for example, to place a fine film of lubricant on metal parts, as buffing abrasive agents to remove buffing abrasive compounds from polished surfaces such as metal, as displacement drying agents for removing water, such as from jewelry or metal parts, as resist developers in conventional circuit manufacturing techniques including chlorine-type developing agents, or as strippers for photoresists when used with, for example, a chlorohydrocarbon such as 1,1,1-trichloroethane or trichloroethylene.
The present invention relates to the discovery of compositions of perfluorooxetane (C-216E) and perfluoromethyl ethyl ether (218E) or dimethyl ether (DME); 2,2,4,4,5,5-hexafluoro-1,3-dioxolane (C-216E2) and cyclopropane or dimethyl ether (DME); 2,2,3,4,4-pentafluorooxetane (C-225eEαβ) and difluoromethyl(trifluoromethyl)sulfide (125S) or 1-trifluoromethoxy-2,2,2-trifluoroethane (236faE); 2,2,4,4-tetrafluorooxetane (C-234fEαβ) and 1-difluoromethoxy-1,1,2,2-tetrafluoroethane (236caE) or 1-difluoromethoxy-1,2,2,2-tetrafluoroethane (236eaEβγ); 2,2,3,3-tetrafluorooxetane (C-234fEβγ) and 1-difluoromethoxy-1,1,2,2-tetrafluoroethane (236caE) or 1-difluoromethoxy-1,2,2,2-tetrafluoroethane (236eaEβγ). This invention also relates to the discovery of azeotropic or azeotrope-like compositions comprising effective amounts of these compositions to form azeotropic or azeotrope-like compositions.
These compositions, which have little or no ozone depletion potential and which present environmentally acceptable alternatives to CFCs and HCFCs, are useful as refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.
FIG. 1 is a graph of the vapor/liquid equilibrium curve for mixtures of C-216E/218E at 25° C.;
FIG. 2 is a graph of the vapor/liquid equilibrium curve for mixtures of C-216E/DME at 25° C.;
FIG. 3 is a graph of the vapor/liquid equilibrium curve for mixtures of C-216E2/cyclopropane at 25° C.;
FIG. 4 is a graph of the vapor/liquid equilibrium curve for mixtures of C-216E2/DME at 25° C.;
FIG. 5 is a graph of the vapor/liquid equilibrium curve for mixtures of C-225eEαβ/125S at 25° C.;
FIG. 6 is a graph of the vapor/liquid equilibrium curve for mixtures of C-225eEαβ/236faE at 25° C.;
FIG. 7 is a graph of the vapor/liquid equilibrium curve for mixtures of C-234fEαβ/236cae at 25° C.;
FIG. 8 is a graph of the vapor/liquid equilibrium curve for mixtures of C-234fEαβ/236eaEβγ at 25° C.;
FIG. 9 is a graph of the vapor/liquid equilibrium curve for mixtures of C-234fEβγ/236caE at 25° C.; and
FIG. 10 is a graph of the vapor/liquid equilibrium curve for mixtures of C-234fEβγ/236eaEβγ at 25° C.
The present invention relates to the discovery of compositions of C-216E and 218E or DME; C-216E2 and cyclopropane or DME; C-225eEαβ and 125S or 236faE; C-234fEαβ and 236caE or 236eaEβγ; C-234fEβγ and 236caE or 236eaEβγ. This invention also relates to the discovery of azeotropic or azeotrope-like compositions comprising effective amounts of these compositions to form azeotropic or azeotrope-like compositions. 1-99 wt. % of each of the above components can be used as refrigerants.
The components of the refrigerants in this invention include the following:
1. Perfluorooxetane (C-216E or ##STR1## boiling point=-29.2° C.), 2. 2,2,4,4,5,5-hexafluoro-1,3-dioxolane (C-216E2 or C3 F6 O2, having a structure of ##STR2## boiling point=-22.1° C.), 3. 2,2,3,4,4-pentafluorooxetane (C-225eEαβ, or C3 HF5 O, having a structure of ##STR3## boiling point=3.4° C.), 4. 2,2,4,4-tetrafluorooxetane (C-234fEαβ, or C3 H2 F4, having a structure of ##STR4## boiling point=21.2° C.), 5. 2,2,3,3-tetrafluorooxetane (C-234fEβγ, or C3 H2 F4 O, having a structure of ##STR5## boiling point=28° C.), 6. Perfluoromethyl ethyl ether (218E, or CF3 OCF2 CF3, boiling point=-23.3° C.),
7. Dimethyl ether (DME, or CH3 OCH3),
9. difluoromethyl(trifluoromethyl)sulfide (125S or CHF2 SCF3, boiling point=1.0° C.)
10. 1-trifluoromethoxy-2,2,2-trifluoroethane (236faE, or CF3 OCH2 CF3, boiling point=5.6° C.),
11. 1-difluoromethoxy-1,1,2,2-tetrafluoroethane (236caE, or CHF2 OCF2 CHF2, boiling point=28.5° C.), and
12. 1-difluoromethoxy-1,2,2,2-tetrafluoroethane (236eaEβγ, or CHF2 OCHFCF3, boiling point=23.2° C.).
C-216E (CAS Reg. No. 425-82-1) can be made by electrochemical fluorination of trimethylene oxide (oxetane) in anhydrous hydrogen fluoride as disclosed by Kauck and Simons in U.S. Pat. No. 2,594,272.
C-216E2 (CAS Reg. No. 21297-65-4) has been prepared by UV irradiation of perfluoro-b-oxa-d-valerolactone in the vapor or liquid phase as reported by Throckmorton in J. Org.Chem., Vol. 34, pp. 3438-3440 (1969). The lactone was prepared by the reaction of KF with perfluorooxydiacetyl chloride.
C-225eEαβ (CAS Reg. No. 144109-03-5) may be prepared by direct fluorination of trimethylene oxide (cyclo-CH2 CH2 CH2 O--) using techniques described by Lagow and Margrave in Progress in Inorganic Chemistry., Vol. 26, pp. 161-210 (1979) or by Adcock and Cherry in Ind. Eng. Chem. Res., Vol. 26, pp. 208-215 (1987). The direct fluorination is carried out to the desired level of fluorine incorporation into the starting material, and products recovered by fractional distillation.
C-234fEαβ may be prepared by direct fluorination of trimethylene oxide(cyclo-CH2 CH2 CH2 O--) using techniques described by Lagow and Margrave in Progress in Inorganic Chemistry, Vol. 26, pp. 161-210 (1979) or by Adcock and Cherry in Ind. Eng. Chem. Res., Vol. 26, pp. 208-215 (1987). The direct fluorination is carried out to the desired level of fluorine incorporation into the starting material, and products recovered by fractional distillation.
C-234fEβγ (CAS Reg. No. 765-63-9) has been prepared by Weinmayr (J. Or Chem., Vol. 28, pp. 492-494 (1963)) as a by-product from the reaction of TFE with formaldehyde in HF.
218E (CAS Reg. No. 665-16-7) has been made by direct fluorination of CF3 OCH2 CF3 (prepared by reaction of CF3 OF with vinylidene fluoride) as reported by Sekiya and Ueda in Chemistry Letters, pp. 609-612 (1990).
125S (CAS Reg. No. 371-72-2) has been prepared by the photolysis of CF2 HC(O)OSCF3 as described by Yu et. al. in Inorg. Chem., Vol. 13, pages 484-486 (1974).
236faE (CAS Reg. No. 20193-67-3) has been prepared by reaction of 2,2,2-trifluoroethanol with carbonyl fluoride to give the intermediate, CF3 CH2 OCOF, which was in turn reacted with sulfur tetrafluoride at 150°-200° C. to give the product as disclosed by Eisemann in U.S. Pat. No. 3,394,878.
236caE (CAS Reg. No. 32778-11-3) has been prepared by fluorination of CHCl2 OCF2 CHF2 (prepared in turn by chlorination of CH3 OCF2 CHF2) using anhydrous hydrogen fluoride with antimony pentachloride catalyst as reported by Terrell, et. al. in J. Medicinal Chem., Vol. 15, pp. 604-606 (1972).
236eaEβγ (CAS Reg. No. 5704 1-67-5) has been prepared by chlorination of methoxy acetyl chloride to give the intermediate, CHCl2 OCHC1 COCl, which was isolated and reacted with sulfur tetrafluoride at 150° C. to give the product as disclosed by Halpern and Robin in U.S. Pat. No. 4,888,139.
The present invention also relates to the discovery of azeotropic or azeotrope-like compositions of effective amounts of C-216E and 218E or DME; C-216E2 and cyclopropane or DME; C-225eEαβ and 125S or 236faE; C-234fEαβ and 236caE or 236eaEβγ; C-234fEβγ and 236caE or 236eaEβγ to form an azeotropic or azeotrope-like composition.
By "azeotropic" composition is meant a constant boiling liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it was evaporated or distilled., that is, the admixture distills/refluxes without compositional change. Constant boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixtures of the same components.
By "azeotrope-like" composition is meant a constant boiling, or substantially constant boiling, liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change. Another way to characterize an azeotrope-like composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same.
It is recognized in the art that a composition is azeotrope-like if, after 50 weight percent of the composition is removed such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than 10 percent, when measured in absolute units. By absolute units, it is meant measurements of pressure and, for example, psia, atmospheres, bars, torr, dynes per square centimeter, millimeters of mercury, inches of water and other equivalent terms well known in the art. If an azeotrope is present, there is no difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed.
Therefore, included in this invention are compositions of effective amounts of C-216E and 218E or DME; C-216E2 and cyclopropane or DME; C-225eEαβ and 125S or 236faE; C-234fEαβ and 236caE or 236eaEβγ; C-234fEαβ an 236caE or 236eaEβγ, such that after 50 weight percent of an original composition is evaporated or boiled off to produce a remaining composition, the difference in the vapor pressure between the original composition and the remaining composition is 10 percent or less.
For compositions that are azeotropic, there is usually some range of compositions around the azeotrope point that, for a maximum boiling azeotrope, have boiling points at a particular pressure higher than the pure components of the composition at that pressure and have vapor pressures at a particular temperature lower than the pure components of the composition at that temperature, and that, for a minimum boiling azeotrope, have boiling points at a particular pressure lower than the pure components of the composition at that pressure and have vapor pressures at a particular temperature higher than the pure components of the composition at that temperature. Boiling temperatures and vapor pressures above or below that of the pure components are caused by unexpected intermolecular forces between and among the molecules of the compositions, which can be a combination of repulsive and attractive forces such as van der Waals forces and hydrogen bonding.
The range of compositions that have a maximum or minimum boiling point at a particular pressure, or a maximum or minimum vapor pressure at a particular temperature, may or may not be coextensive with the range of compositions that have a change in vapor pressure of less than about 10% when 50 weight percent of the composition is evaporated. In those cases where the range of compositions that have maximum or minimum boiling temperatures at a particular pressure, or maximum or minimum vapor pressures at a particular temperature, are broader than the range of compositions that have a change in vapor pressure of less than about 10% when 50 weight percent of the composition is evaporated, the unexpected intermolecular forces are nonetheless believed important in that the refrigerant compositions having those forces that are not substantially constant boiling may exhibit unexpected increases in the capacity or efficiency versus the components of the refrigerant composition.
The components of the compositions of this invention have the following vapor pressures at 25° C.
______________________________________Components Psia kPa______________________________________C-216E 100.3 692C-216E2 76.7 529C-225eEαβ 31.1 214C-234fEαβ 16.7 115C-234fEβγ 13.3 91218E 83.8 578DME 85.7 591125S 34.5 238236faE 29.6 204236caE 12.9 89236eaEβγ 15.7 108cyclopropane 105.0 724______________________________________
Substantially constant boiling, azeotropic or azeotrope-like compositions of this invention comprise the following (all compositions are measured at 25° C.):
______________________________________ WEIGHT RANGES PREFERREDCOMPONENTS (wt. %/wt/%) (wt. %/wt. %)______________________________________C-216E/218E 1-99/1-99 20-99/1-80C-216E/DME 1-99/1-99 20-99/1-80C-216E2/cyclopropane 0.9-99/1-99.1 0.9-99/1-99.1C-216E2/DME 1-99/1-99 20-99/1-80C-225eEαβ/125S 1-99/1-99 1-80/20-99C-225eEαβ/236faE 1-99/1-99 1-99/1-99C-234fEαβ/236caE 1-99/1-99 15-99/1-85C-234fEαβ/236eaEβγ 1-99/1-99 1-99/1-99C-234fEβγ/236caE 1-99/1-99 1-99/1-99C-234fEβγ/236eaEβγ 1-99/1-99 1-80/20-99______________________________________
For purposes of this invention, "effective amount" is defined as the amount of each component of the inventive compositions which, when combined, results in the formation of an azeotropic or azeotrope-like composition. This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotropic or azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points.
Therefore, effective amount includes the amounts, such as may be expressed in weight percentages, of each component of the compositions of the instant invention which form azeotropic or azeotrope-like compositions at temperatures or pressures other than as described herein.
For the purposes of this discussion, azeotropic or constant-boiling is intended to mean also essentially azeotropic or essentially-constant boiling. In other words, included within the meaning of these terms are not only the true azeotropes described above, but also other compositions containing the same components in different proportions, which are true azeotropes at other temperatures and pressures, as well as those equivalent compositions which are part of the same azeotropic system and are azeotrope-like in their properties. As is well recognized in this art, there is a range of compositions which contain the same components as the azeotrope, which will not only exhibit essentially equivalent properties for refrigeration and other applications, but which will also exhibit essentially equivalent properties to the true azeotropic composition in terms of constant boiling characteristics or tendency not to segregate or fractionate on boiling.
It is possible to characterize, in effect, a constant boiling admixture which may appear under many guises, depending upon the conditions chosen, by any of several criteria:
The composition can be defined as an azeotrope of A, B, C (and D . . . ) since the very term "azeotrope" is at once both definitive and limitative, and requires that effective amounts of A, B, C (and D . . . ) for this unique composition of matter which is a constant boiling composition.
It is well known by those skilled in the art, that, at different pressures, the composition of a given azeotrope will vary at least to some degree, and changes in pressure will also change, at least to some degree, the boiling point temperature. Thus, an azeotrope of A, B, C (and D . . . ) represents a unique type of relationship but with a variable composition which depends on temperature and/or pressure. Therefore, compositional ranges, rather than fixed compositions, are often used to define azeotropes.
The composition can be defined as a particular weight percent relationship or mole percent relationship of A, B, C (and D . . . ), while recognizing that such specific values point out only one particular relationship and that in actuality, a series of such relationships, represented by A, B, C (and D . . . ) actually exist for a given azeotrope, varied by the influence of pressure.
An azeotrope of A, B, C (and D . . . ) can be characterized by defining the compositions as an azeotrope characterized by a boiling point at a given pressure, thus giving identifying characteristics without unduly limiting the scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available.
The azeotrope or azeotrope-like compositions of the present invention can be prepared by any convenient method including mixing or combining the desired amounts. A preferred method is to weigh the desired component amounts and thereafter combine them in an appropriate container.
Specific examples illustrating the invention are given below. Unless otherwise stated therein, all percentages are by weight. It is to be understood that these examples are merely illustrative and in no way are to be interpreted as limiting the scope of the invention.
A phase study shows the following compositions are azeotropic, all at 25° C.
______________________________________ Weight percent of Vapor Press.Composition No. the components psia (kPa)______________________________________C-216E/218E 81.9/18.1 101.2 698C-216E/DME 82.1/17.9 111.2 767C-216E2/cyclopropane 0.9/99.1 105. 724C-216E2/DME 69.2/30.8 97.5 672C-225eEαβ/125S 7.2/92.8 34.5 238C-225eEαβ/236faE 64.9/35.1 31.7 219C-234fEαβ/236caE 90.7/9.3 16.8 116C-234fEαβ/236eaEβγ 57.5/42.5 17.8 123C-234fEβγ/236caE 51.8/48.2 14.4 99C-234fEβγ/236eaEβγ 28.6/71.4 16.3 112______________________________________
Impact of Vapor Leakage on Vapor Pressure at 25° C.
A vessel is charged with an initial composition at 25° C., and the vapor pressure of the composition is measured. The composition is allowed to leak from the vessel, while the temperature is held constant at 25° C., until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured. The results are summarized below.
______________________________________ INITIAL 50% LEAK DELTAWT % A/WT % B PSIA KPA PSIA KPA % P______________________________________C-216E/218E81.9/18.1 101.2 698 101.2 698 0.090./10 101. 696 101. 696 0.099/1 100.4 692 100.4 692 0.060/40 100.1 690 99.9 689 0.240/60 97.1 669 96.3 664 0.820/80 91.9 634 90.7 625 1.310/90 88.3 609 87.3 602 1.11/99 84.3 581 84.2 581 0.1C-216E/DME82.1/17.9 111.2 767 111.2 767 0.099/1 102.1 704 101.6 701 0.560/40 107.6 742 105.3 726 2.140/60 101.9 703 96.4 665 5.430/70 98.4 678 92.4 637 6.120/80 94.6 652 89.3 616 5.61/99 86.2 594 85.8 592 0.5C-216E2/cyclopropane0.9/99.1 105. 724 105. 724 0.030/70 104.7 722 104.7 722 0.070/30 100.7 694 99.7 687 1.85/15 94.9 654 92.6 638 2.499/1 78.8 543 78.1 538 0.9C-216E2/DME69.2/30.8 97.5 672 97.5 672 0.085/15 95.1 656 93.8 647 1.499/1 79.4 547 78.2 539 1.540/60 94.6 652 93.0 641 1.720/80 90.7 625 88.7 612 3.31/99 86.0 593 85.8 592 0.2C-225eEαβ/125S7.2/92.8 34.5 238 34.5 238 0.01/99 34.5 238 34.5 238 0.030/70 34.3 236 34.3 236 0.060/40 33.5 231 33.4 230 0.380/20 32.5 224 32.4 223 0.399/1 31.2 215 31.2 215 0.0C-225eEαβ/236faE64.9/35.1 31.7 219 31.7 219 0.080/20 31.6 218 31.6 218 0.099/1 31.1 214 31.1 214 0.030/70 31.1 214 31.1 214 0.01/99 29.7 205 29.7 205 0.0C-234fEαβ/236caE90.7/9.3 16.8 116 16.8 116 0.099/1 16.8 116 16.8 116 0.060/40 16.4 113 16.3 112 0.630/70 15.2 105 14.9 103 2.15/85 14.3 99 14. 97 2.11/99 13. 90 13. 90 0.0C-234fEαβ/236eaEβγ 17.8 123 17.8 123 0.057.5/42.580/20 17.5 121 17.5 121 0.099/1 16.8 116 16.8 116 0.020/80 17. 117 16.9 117 0.61/99 15.8 109 15.8 109 0.0C-234fEβγ/236caE51.8/48.2 14.4 99 14.4 99 0.025/75 14. 97 14. 97 0.01/99 13. 90 13. 90 0.075/25 14.1 97 14.1 97 0.099/1 13.3 92 13.3 92 0.0C-234fEβγ/236eaEβγ28.6/71.4 16.3 112 16.3 112 0.015/85 16.2 112 16.2 112 0.01/99 15.7 108 15.7 108 0.060/40 15.8 109 15.6 108 1.380/20 14.9 103 14.5 100 2.799/1 13.4 92 13.3 92 0.7______________________________________
The results of this Example show that these compositions are azeotropic or azeotrope-like because when 50 wt. % of an original composition is removed, the vapor pressure of the remaining composition is within about 10% of the vapor pressure of the original composition, at a temperature of 25° C.
Impact of Vapor Leakage at 50° C.
A leak test is performed on composition of C-216E and DME, at the temperature of 50° C. The results are summarized below.
______________________________________ INITIAL 50% LEAK DELTAWT % A/WT % B PSIA KPA PSIA KPA % P______________________________________C216E/DME82.7/17.3 212.0 1462 212.0 1462 0.099/1 197.0 1358 196.2 1353 0.460/40 205.0 1413 201.0 1386 2.040/60 194.3 1340 185.1 1276 4.720/80 181.1 1249 172.5 1189 4.71/99 166.4 1147 165.8 1143 0.4______________________________________
The following table shows the performance of various refrigerants. The data are based on the following conditions.
Evaporator temperature 48.0° F. (8.9° C.)
Condenser temperature 115.0° F. (46.1° C.)
Subcooled 12.0° F. (6.7° C.)
Return gas temperature 65.0° F. (18.3° C.)
Compressor efficiency is 75%.
The refrigeration capacity is based on a compressor with a fixed displacement of 3.5 cubic feet per minute and 75% volumetric efficiency. Capacity is intended to mean the change in enthalpy of the refrigerant in the evaporator per pound of refrigerant circulated, i.e. the heat removed by the refrigerant in the evaporator per time. Coefficient of performance (COP) is intended to mean the ratio of the capacity to compressor work. It is a measure of refrigerant energy efficiency.
__________________________________________________________________________ Evap. Cond. CapacityRefrig. Press. Press. Comp. Dis. BTU/minComp. Psia (kPa) Psia (kPa) Temp. °F. (°C.) COP (kw)__________________________________________________________________________C-216E/218E5.0/95.0 51 (352) 154 (1062) 122 (50) 4.06 189 (3.3)81.9/18.1 57 (393) 161 (1110) 123 (50.6) 4.15 205 (3.6)95.0/5.0 58 (400) 163 (1124) 123 (50.6) 4.17 208 (3.7)C-216E/DME5.0/95.0 54 (372) 155 (1069) 165 (73.9) 5.00 254 (4.5)82.1/17.9 83 (572) 221 (1524) 135 (57.2) 4.26 291 (5.1)95.0/5.0 69 (476) 190 (1310) 128 (53.3) 4.25 248 (4.4)C-216E2/cyclopropane0.9/99.1 66 (455) 178 (1227) 174 (78.9) 4.87 289 (5.1)95.0/5.0 53 (365) 154 (1062) 125 (51.7) 4.43 213 (3.8)C-216E2/DME5.0/95.0 52 (359) 150 (1034) 166 (74.4) 4.88 242 (4.3)69.2/30.8 61 (421) 172 (1186) 140 (60.0) 4.63 254 (4.5)95.0/5.0 52 (359) 153 (1055) 124 (51.1) 4.41 209 (3.7)C-225eEαβ/125S1.0/99.0 20 (138) 66 (455) 139 (59.4) 4.85 102 (1.8)7.2/92.8 19 (131) 66 (455) 138 (58.9) 4.85 101 (1.8)95.0/5.0 18 (124) 59 (407) 130 (54.4) 4.82 91 (1.6)C-225eEαβ/236faE5.0/95.0 17 (117) 59 (407) 127 (52.8) 4.71 86 (1.5)64.9/35.1 17 (117) 59 (407) 129 (53.9) 4.78 89 (1.6)95.0/5.0 18 (124) 59 (407) 130 (54.4) 4.82 90 (1.6)C-234fEαβ/236caE5.0/95.0 7 (48) 28 (193) 134 (56.7) 4.91 42 (0.7)90.7/9.3 9 (62) 32 (221) 135 (57.2) 4.96 51 (0.9)99.0/1.0 9 (62) 33 (228) 135 (57.2) 4.97 51 (0.9)C-234fEαβ/236eaEβγ5.0/95.0 8 (55) 33 (228) 133 (56.1) 4.88 50 (0.9)57.5/42.5 9 (62) 33 (228) 134 (56.7) 4.93 50 (0.9)95.0/5.0 9 (62) 33 (228) 135 (57.2) 4.96 52 (0.9)C-234fEβγ/236caE5.0/95.0 7 (48) 27 (186) 134 (56.7) 4.91 41 (0.7)51.8/48.2 7 (48) 28 (193) 135 (57.2) 4.96 43 (0.8)95.0/5.0 7 (48) 26 (179) 137 (58.3) 4.99 42 (0.7)C-234fEβγ/236eaEβγ5.0/95.0 8 (55) 33 (228) 133 (56.1) 4.88 49 (0.9)28.6/71.4 8 (55) 31 (214) 134 (56.7) 4.92 48 (0.8)95.0/5.0 7 (48) 26 (179) 137 (58.3) 4.99 42 (0.7)__________________________________________________________________________
This Example is directed to measurements of the liquid/vapor equilibrium curves for the mixtures in FIGS. 1-10.
Turning to FIG. 1, the upper curve represents the composition of the liquid, and the lower curve represents the composition of the vapor.
The data for the compositions of the liquid in FIG. 1 are obtained as follows. A stainless steel cylinder is evacuated, and a weighed amount of C-216E is added to the cylinder. The cylinder is cooled to reduce the vapor pressure of C-216E, and then a weighed amount of 218E is added to the cylinder. The cylinder is agitated to mix the C-216E and 218E, and then the cylinder is placed in a constant temperature bath until the temperature comes to equilibrium at 25° C., at which time the vapor pressure of the C-216E and 218E in the cylinder is measured. Additional samples of liquid are measured the same way, and the results are plotted in FIG. 1.
The curve which shows the composition of the vapor is calculated using an ideal gas equation of state.
Vapor/liquid equilibrium data are obtained in the same way for the mixtures shown in FIGS. 2-10.
The data in FIGS. 1-10 show that at 25° C., there are ranges of compositions that have vapor pressures higher than the vapor pressures of the pure components of the composition at that same temperature. As stated earlier, the higher than expected pressures of these compositions may result in an unexpected increase in the refrigeration capacity and efficiency for these compositions versus the pure components of the compositions.
The compositions of this invention, including the azeotropic or azeotrope-like compositions, may be used to produce refrigeration by condensing the compositions and thereafter evaporating the condensate in the vicinity of a body to be cooled. These compositions may also be used to produce heat by condensing the refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant.
The novel compositions of the invention are particularly suitable for replacing refrigerants that may affect the ozone layer, including R-11, R-12, R-22, R-114 and R-502.
In addition to refrigeration applications, the compositions of this invention, including the azeotropic or azeotrope-like compositions, are also useful as aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, expansion agents for polyolefins and polyurethanes and power cycle working fluids.
Other components, such as aliphatic hydrocarbons having a boiling point of -60° to +60° C., hydrofluorocarbonalkanes having a boiling point of -60° to +60° C., hydrofluoropropanes having a boiling point of between -60° to +60° C., hydrocarbon esters having a boiling point between -60° to +60° C., hydrochlorofluorocarbons having a boiling point between -60° to +60° C., hydrofluorocarbons having a boiling point of -60° to +60° C., hydrochlorocarbons having a boiling point between -60° to +60° C., chlorocarbons and perfluorinated compounds, can be added to the azeotropic or azeotrope-like compositions described above without substantially changing the properties thereof, including the constant boiling behavior, of the compositions.
Additives such as lubricants, corrosion inhibitors, surfactants, stabilizers, dyes and other appropriate materials may be added to the novel compositions of the invention for a variety of purposes provides they do not have an adverse influence on the composition for its intended application. Preferred lubricants include esters having a molecular weight greater than 250.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2594272 *||Sep 10, 1948||Apr 29, 1952||Minnesota Mining & Mfg||Cyclic fluoroalkylene oxide compounds|
|US3362180 *||Aug 25, 1965||Jan 9, 1968||Du Pont||Chemical process|
|US4541943 *||May 16, 1984||Sep 17, 1985||Imperial Chemical Industries Plc||Heat pumps|
|US4886581 *||Jul 1, 1987||Dec 12, 1989||Daikin Industries Ltd.||Removal of hydrogen fluoride from 2,2,3,3-tetra-fluorooxetane|
|US4946972 *||Jan 23, 1989||Aug 7, 1990||Daikin Industries, Ltd.||Process for distillation of 2,2,3,3-tetrafluorooxetane|
|US5137932 *||Dec 5, 1990||Aug 11, 1992||Hoechst Aktiengesellschaft||Process for producing foams|
|US5166182 *||Mar 23, 1992||Nov 24, 1992||Atlas Roofing Corporation||Thermosetting plastic foams and methods of production thereof using novel blowing agents|
|US5248795 *||Dec 9, 1991||Sep 28, 1993||Electric Power Research Institute||3-hydryl-f-oxetane and 3,3-dihydryl-f-oxetane compounds useful as refrigerants or solvents|
|US5264462 *||Mar 1, 1993||Nov 23, 1993||Imperial Chemical Industries Plc||Polymeric foams|
|EP0416777A2 *||Aug 22, 1990||Mar 13, 1991||Imperial Chemical Industries Plc||Polymeric foams|
|EP0510295A2 *||Jan 11, 1992||Oct 28, 1992||Halocarbon Products Corporation||Ozone safe refrigerants and blowing agents|
|JPH04110385A *||Title not available|
|JPH04110386A *||Title not available|
|WO1993004138A1 *||Aug 25, 1992||Mar 4, 1993||E.I. Du Pont De Nemours And Company||Chlorine-free fluorocarbon refrigerant|
|WO1993012102A1 *||Dec 4, 1992||Jun 24, 1993||Electric Power Research Institute, Inc.||3-hydryl-f-oxetane and 3,3-dihydryl-f-oxetane compounds useful as refrigerants or solvents|
|WO1993024586A1 *||May 20, 1993||Dec 9, 1993||E.I. Du Pont De Nemours And Company||Compositions of a fluoroether and a hydrofluorocarbon|
|1||Adcock et al., Fluorinated Ethers: A "New" Series of CFC Substitutes, University of Tennessee, Jan. 28 to Feb. 2, 1991.|
|2||*||Adcock et al., Fluorinated Ethers: A New Series of CFC Substitutes, University of Tennessee, Jan. 28 to Feb. 2, 1991.|
|3||*||Devotta et al., Assessment of HFCs, Fluorinated Ethers and Amine as Alternatives to CFC12, Int. J. Refrig. , 16, No. 2, 84 90, 1993.|
|4||Devotta et al., Assessment of HFCs, Fluorinated Ethers and Amine as Alternatives to CFC12, Int. J. Refrig., 16, No. 2, 84-90, 1993.|
|5||*||Kopko, Beyond CFCS: Extending the Search for New Refrigerants, ASHRAE CFC Tech. Conf., Gaithersburg, Md., Sep. 27 28, 1989.|
|6||Kopko, Beyond CFCS: Extending the Search for New Refrigerants, ASHRAE CFC Tech. Conf., Gaithersburg, Md., Sep. 27-28, 1989.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5645754 *||Dec 22, 1994||Jul 8, 1997||E. I. Du Pont De Nemours And Company||Compositions including a hexafluoroprpoane and dimethyl ether for heat transfer|
|US5779931 *||Jun 9, 1997||Jul 14, 1998||E. I. Du Pont De Nemours And Company||Azeotrope (like) compositions with difluoromethoxytetrafluoro-propane and pentafluoropropane, and methods of use|
|US6055827 *||Aug 13, 1999||May 2, 2000||Hitachi, Ltd||Refrigerant compressor and refrigerating apparatus|
|US6286334 *||Apr 18, 2000||Sep 11, 2001||Hitachi, Ltd.||Refrigerant compressor and refrigerating apparatus|
|US6546740 *||May 19, 2000||Apr 15, 2003||Clemson University||Ternary refrigerant compositions which contain perfluoroorgano sulfur compounds as replacements for R-22|
|US6574973 *||May 19, 2000||Jun 10, 2003||Electric Power Research Institute, Inc.||Ternary refrigerant compositions containing fluorinated ethers as replacements for R-22|
|US7695524||Apr 13, 2010||Whirlpool Corporation||Non-aqueous washing machine and methods|
|US7739891||Jun 22, 2010||Whirlpool Corporation||Fabric laundering apparatus adapted for using a select rinse fluid|
|US7837741||Apr 12, 2005||Nov 23, 2010||Whirlpool Corporation||Dry cleaning method|
|US7966684||Jun 28, 2011||Whirlpool Corporation||Methods and apparatus to accelerate the drying of aqueous working fluids|
|US8262741||Sep 11, 2012||Whirlpool Corporation||Non-aqueous washing apparatus and method|
|US20010032960 *||Feb 9, 2000||Oct 25, 2001||Grzyll Lawrence Robert||Fire extinguishing methods and blends utilizing unsaturated perfluorocarbons|
|US20020056163 *||Dec 20, 2001||May 16, 2002||Estes Kurt A.||Non aqueous washing apparatus and method|
|US20040117919 *||Oct 31, 2003||Jun 24, 2004||Conrad Daniel C.||Non-aqueous washing machine & methods|
|US20050071928 *||Oct 1, 2004||Apr 7, 2005||Wright Tremitchell L.||Non-aqueous washing apparatus and method|
|US20050091755 *||Oct 31, 2003||May 5, 2005||Conrad Daniel C.||Non-aqueous washing machine & methods|
|US20050091756 *||Oct 31, 2003||May 5, 2005||Tremitchell Wright||Non-aqueous washing machine & methods|
|US20050092033 *||Oct 1, 2004||May 5, 2005||Luckman Joel A.||Fabric laundering apparatus adapted for using a select rinse fluid|
|US20050092352 *||Oct 1, 2004||May 5, 2005||Luckman Joel A.||Non-aqueous washing apparatus and method|
|US20050096242 *||Oct 1, 2004||May 5, 2005||Luckman Joel A.||Method for laundering fabric with a non-aqueous working fluid using a select rinse fluid|
|US20050096243 *||Oct 1, 2004||May 5, 2005||Luckman Joel A.||Fabric laundering using a select rinse fluid and wash fluids|
|US20050150059 *||Dec 7, 2004||Jul 14, 2005||Luckman Joel A.||Non-aqueous washing apparatus and method|
|US20050222002 *||May 23, 2005||Oct 6, 2005||Luckman Joel A||Method for a semi-aqueous wash process|
|US20050224099 *||Apr 13, 2004||Oct 13, 2005||Luckman Joel A||Method and apparatus for cleaning objects in an automatic cleaning appliance using an oxidizing agent|
|US20050263173 *||May 23, 2005||Dec 1, 2005||Luckman Joel A||Method for fluid recovery in a semi-aqueous wash process|
|US20060260065 *||May 23, 2005||Nov 23, 2006||Wright Tremitchell L||Methods and apparatus to accelerate the drying of aqueous working fluids|
|US20080189872 *||Oct 1, 2004||Aug 14, 2008||Wright Tremitchell L||Non-aqueous washing apparatus and method|
|U.S. Classification||252/67, 510/177, 510/506, 252/8, 516/10, 264/DIG.5, 252/194, 510/411, 252/571, 62/114, 516/8, 134/40|
|International Classification||C07D317/42, C08G18/08, C08J9/14, C07C323/01, C09K3/30, C07C43/12, C07D303/08, C07C13/04, F25B1/00, C09K5/04|
|Cooperative Classification||C09K2205/11, C09K5/045, C09K2205/12, C09K2205/112, Y10S264/05, C08J9/143, C09K2205/116, C08J9/149, C09K2205/22, C08J2203/146, C09K2205/134, C08J2203/14|
|European Classification||C08J9/14P, C08J9/14H, C09K5/04B4B|
|Jun 24, 1994||AS||Assignment|
Owner name: E.I. DU PONT DE NEMOURS AND COMPANY, DELAWARE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MINOR, BARBARA HAVILAND MINOR;REEL/FRAME:007036/0602
Effective date: 19940512
|Jul 27, 1999||REMI||Maintenance fee reminder mailed|
|Jan 2, 2000||LAPS||Lapse for failure to pay maintenance fees|
|Mar 14, 2000||FP||Expired due to failure to pay maintenance fee|
Effective date: 20000102